Trajectory studies of S(N)2 nucleophilic substitution. 8. Central barrier dynamics for gas phase Cl(-) + CH(3)Cl

Quasiclassical direct dynamics trajectories, calculated at the MP2/6-31G level of theory, are used to study the central barrier dynamics for the C1(-) + CH(3)Cl S(N)2 reaction. Extensive recrossings of the central barrier are observed in the trajectories. The dynamics of the Cl(-)-CH(3)Cl complex is non-RRKM and transition state theory (TST) is predicted to be an inaccurate model for calculating the Cl(-) + CH(3)Cl S(N)2 rate constant. Direct dynamics trajectories also show that Cl(-) + CH(3)Cl trajectories, which collide backside along the S(N)2 reaction path, do not form the Cl(-)-CH(3)Cl complex. This arises from weak coupling between the Cl(-)-CH(3)Cl intermolecular and CH(3)Cl intramolecular modes. The trajectory results are very similar to those of a previous trajectory study, based on a HF/6-31G* analytic potential energy function, which gives a less accurate representation of the central barrier region of the Cl(-) + CH(3)Cl reaction than does the MP2/6-31G* level of theory used here. Experiments are suggested for investigating the non-RRKM and non-TST dynamics predicted by the trajectories.     

ENVIRONMENTAL STABILITY OF THE POLYENE PREPARED BY DEHYDROCHLORINATION OF POLY(VINYL CHLORIDE)

A high-quality polyene can be obtained by exensive dehydrochlorination of poly(vinyl chloride) (PVC) in aliquid/solid two-phase system. The liquid phase is a tetrahydrofuran solution of PVC containing a small amount ofpoly(ethylene glycol) with molar mass of 400 g as a phase transfer catalys. The solid phase is potassium hydroxide particles.The structure of the polyene is polyacetylene-like and has a long conjugated C=C sequence and a narrow dispersity ofpolyene sequences according to its FT-infrared and Raman spectra. The environmental stability of the polyene was alsostudied by IR, Raman spectra and elemental analysis. Experimental results demonstrated that the polyene was susceptible toair and could be changed into a material containing high concentrations of hydroxyl and carbonyl groups. The polyenesequences were shortened and its dispersity became broader due to the effect of dioxygen.     

催化极谱法连续测定岩石中钨和钼

本文提出了在二苯基乙醇酸-二苯胍-氯酸钠催化极谱体系测钨后,加入少许钛铁试剂,使钼产生一个极灵敏的导数波。谊波形尖锐、对称,便于测量钼。建立的连测体系简便灵敏,用于岩石样品中钨和钼的测定,取得了满意的效果。     

使用疏水作用色谱研究蛋白质的构象变化

研究了高效疏水作用液相色谱中(HIC)色谱条件改变对蛋白质构象的影响。发现固定相配体的疏水性、温度及流动相中盐的阴离子、阳离子和pH值都影响蛋白质的构象。     

Semipreparative separation and determination of eleutheroside E in Acanthopanax giraldii Harms by high-performance liquid chromatography

A method for the isolation, purification, and determination of eleutheroside E in Acanthopanax giraldii Harms, collected in the Sichuan province (China), is established. The water extraction of A. giraldii Harms is pre-isolated using macroporous adsorption resin (D-101) and a C18 solid-phase extraction cartridge, and the enriched extract is purified to give eleutheroside E (syringaresinol-di-O-beta-D-glucoside; liriodendrin) by semipreparative reversed-phase high-performance liquid chromatography. Structure identification is performed by a comparison of IR, 1H-NMR, 13C-NMR, and electrospray ionization-mass spectrometric data with the literature. The final purity of the compound is 97%. Quantitative determination of eleutheroside E in A. giraldii Harms is performed on a Zorbax SB C18 (150- x 4.6-mm i.d., 5 microm) column. The linear range of eleutheroside E is 4.85-194 mg/L (r = 0.9998), and the average recovery is 99.6-101%. The developed method is simple, reproducible, and easy to operate. It is useful for the evaluation of Acanthopanax giraldii Harms.     

Enthalpies of dilution of l-cystine in aqueous solutions of sodium hydroxide, potassium hydroxide and hydrochloric acid

The enthalpies of dilution of l-cystine in solutions of two strong alkalis and one strong acid have been determined by isothermal flow-mix calorimetry at the temperatures 298.15 K, 303.15 K, 308.15 K, 313.15 K and 318.15 K. Equations of apparent enthalpies of dilution have been obtained from the experimental data in terms of the improved McMillan-Mayer theory. Enthalpic interaction coefficients, h₂, h₃, and h₄, are obtained and the values of pair-wise enthalpic interaction coefficient, h₂, discussed in the light of solute-solute and solute-solvent interactions.     

Coriatone and corianlactone, two novel sesquiterpenes from Coriaria nepalensis

Both coriatone (1). a novel highly oxygenated picrotoxane-type sesquiterpene, and corianlactone (2). with an unprecedented sesquiterpene basic skeleton, named coriane, were isolated from Coriaria nepalensis Wall. The structures of 1 and 2 were determined by analysis of their two-dimensional NMR data, and the structure of 2 was confirmed by X-ray analysis. Compounds 1 and 2 showed no remarkable inhibitory activity toward K(562) cells. They are cytotoxic with IC(50) > 50 microg/mL (cis-platinim: IC(50) = 0.49 microg/mL).     

SciFinder-guided rational design of fluorescent carbon dots for ratiometric monitoring intracellular pH fluctuations under heat shock

Intracellular pH plays a significant role in various biological processes, including cell proliferation, apoptosis, metabolism, enzyme activity and homeostasis. In this work, a novel design strategy for the preparation of pH responsive carbon dots (CDs-pH) for ratiometric intracellular imaging was reported. By using SciFinder database, fluorescent CDs-pH with the required pK_a value of 6.84 were rationally designed, which is vital important for precise sensing of intracellular pH. As a result, the synthesized CDs-pH demonstrated robust ability to test pH fluctuations within the physiological range of 5.4-7.4. The CDs-pH was further utilized for fluorescent ratiometric imaging of pH in living HeLa cells, effectively avoided the influence of autofluorescence from native cellular species. Moreover, real-time monitoring of intracellular pH fluctuation under heat shock was successfully realized. This SciFinder-guided design strategy is simple and flexible, which has a great potential to be used for the development of other types of CDs for various applications.     

An ionic liquid-type carbon paste electrode and its polyoxometalate-modified properties

The replacement of a non-conductive organic binder with a conductive room temperature ionic liquid in fabricating carbon paste electrode has been made. This new electrode due to its enhanced conductivity presented very large current response from electroactive substrates. The novel carbon paste electrode was bulk-modified via the uniform dispersion of Keggin-type phospho polyoxomolybdate (PMo₁₂) in bulky carbons, which possessed excellent electrocatalytic activity for the reduction of nitrite. The pronounced multi-electron catalytic ability was ascribed to the used hydrophobic ionic liquid which constructed an excellent charge-transfer bridge in the bulk of carbon paste electrode, thus facilitated the intake of electrons from reduced PMo₁₂ mediators. In view of their prominent properties, the carbon paste electrode using ionic liquid binder and its bulk-modified electrode take on good prospects of the application in physical chemistry and electroanalytical chemistry fields.     

UO2、UC2和UCO分子的结构和热力学性质

用密度泛函B3LYP方法,计算了UO2、UC2和UCO分子的结构和热力学函数,计算了固体U的振动内能Ev、振动和电子熵Sev,以及U在不同气氛（O2、C2、CO）中形成UO2、UC2和UCO晶体的ΔHfΘ、ΔSfΘ和ΔGfΘ.结果表明,UO2晶体最稳定.